U.S. patent application number 10/701430 was filed with the patent office on 2004-05-13 for phosphine compounds, transition metal complexes with the compounds contained as ligands therein, and asymmetric synthesis catalysts containing the complexes.
This patent application is currently assigned to TAKASAGO INTERNATIONAL CORPORATION. Invention is credited to Nagasaki, Izuru, Saito, Takao, Shimizu, Hideo.
Application Number | 20040092388 10/701430 |
Document ID | / |
Family ID | 32171350 |
Filed Date | 2004-05-13 |
United States Patent
Application |
20040092388 |
Kind Code |
A1 |
Shimizu, Hideo ; et
al. |
May 13, 2004 |
Phosphine compounds, transition metal complexes with the compounds
contained as ligands therein, and asymmetric synthesis catalysts
containing the complexes
Abstract
Phosphine compounds represented by the following formula (1): 1
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and
R.sup.7 represent substituents, and asymmetric synthesis catalysts
containing transition metal phosphine complexes with the compounds
contained as ligands therein. The novel phosphine compounds
according to the present invention are useful especially as ligands
in transition metal complexes. The transition metal phosphine
complexes are useful as catalysts for asymmetric synthetic
reactions. The novel phosphine compounds useful as ligands can be
prepared by a relatively economical preparation process. Further,
use of these catalysts can afford hydrogenated products with high
optically purity and is also extremely useful from the industrial
standpoint.
Inventors: |
Shimizu, Hideo;
(Hiratsuka-shi, JP) ; Saito, Takao;
(Hiratsuka-shi, JP) ; Nagasaki, Izuru;
(Hiratsuka-shi, JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
TAKASAGO INTERNATIONAL
CORPORATION
Tokyo
JP
|
Family ID: |
32171350 |
Appl. No.: |
10/701430 |
Filed: |
November 6, 2003 |
Current U.S.
Class: |
502/150 ;
502/152; 502/155; 502/162; 540/542; 546/22; 548/413; 564/16;
568/12 |
Current CPC
Class: |
C07B 53/00 20130101;
B01J 31/2428 20130101; B01J 31/2476 20130101; B01J 2531/16
20130101; B01J 2531/822 20130101; C07F 9/5027 20130101; C07F
15/0053 20130101; C07F 15/0046 20130101; B01J 2531/824 20130101;
B01J 2531/821 20130101; B01J 2531/828 20130101; B01J 31/2471
20130101; C07F 9/65683 20130101; B01J 2531/847 20130101; B01J
2231/643 20130101; B01J 2531/827 20130101; B01J 2531/0266 20130101;
C07F 9/65517 20130101; B01J 2231/645 20130101 |
Class at
Publication: |
502/150 ;
502/152; 502/155; 502/162; 540/542; 546/022; 548/413; 564/016;
568/012 |
International
Class: |
B01J 031/00; C07F
009/547; C07F 009/28 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 12, 2002 |
JP |
2002-327889 |
Claims
1. A phosphine compound represented by the following formula (1):
9wherein R.sup.1 and R.sup.2 each independently represents a
hydrogen atom, a substituted or unsubstituted C.sub.1-10 alkyl
group, a substituted or unsubstituted C.sub.1-10 alkoxy group, a
substituted or unsubstituted C.sub.2-10 alkenyl group, a
substituted or unsubstituted di(C.sub.1-5 alkyl)amino group, a
substituted or unsubstituted, 5- to 8-membered cyclic amino group,
a substituted or unsubstituted, 5-to 8-membered alicyclic group, a
substituted or unsubstituted aryl group, a substituted or
unsubstituted aralkyl group, a substituted or unsubstituted
heterocyclic group, a trisubstituted silyl group or a halogen atom;
R.sup.3, R.sup.4, R.sup.5 and R.sup.6 each independently represents
a hydrogen atom, a C.sub.1-5 alkyl group, a C.sub.1-5 alkoxy group,
a di(C.sub.1-5 alkyl)amino group, a 5- to 8-membered cyclic amino
group or a halogen atom; R.sup.7 represents a C.sub.1-5 alkyl
group, a C.sub.1-5 alkoxy group, a di(C.sub.1-5 alkyl)amino group,
a 5- to 8-membered cyclic amino group or a halogen atom; and
R.sup.3 and R.sup.4, R.sup.5 and R.sup.6, and R.sup.6 and R.sup.7
may each be fused together to form a fused benzene ring, a fused,
substituted benzene ring, a trimethylene group, a tetramethylene
group, a pentamethylene group, a methylenedioxy group, an
ethylenedioxy group or a trimethylenedioxy group.
2. A phosphine compound according to claim 1, which is an axially
asymmetric, optically active substance.
3. A primary phosphine compound represented by the following
formula (2): 10wherein R.sup.5 and R.sup.6 each independently
represents a hydrogen atom, a C.sub.1-5 alkyl group, a C.sub.1-5
alkoxy group, a di(C.sub.1-5 alkyl)amino group, a 5- to 8-membered
cyclic amino group or a halogen atom; R.sup.7 represents a
C.sub.1-5 alkyl group, a C.sub.1-5 alkoxy group, a di(C.sub.1-5
alkyl)amino group, a 5- to 8-membered cyclic amino group or a
halogen atom; and R.sup.5 and R.sup.6, and R.sup.6 and R.sup.7 may
each be fused together to form a fused benzene ring, a fused,
substituted benzene ring, a trimethylene group, a tetramethylene
group, a pentamethylene group, a methylenedioxy group, an
ethylenedioxy group or a trimethylenedioxy group.
4. A primary phosphine compound according to claim 3, which is an
axially asymmetric, optically active substance.
5. A transition metal phosphine complex with a phosphine compound
according to claim 1 or 2 contained as a ligand therein.
6. A transition metal phosphine complex obtained by causing a
transition metal compound to act on a phosphine compound according
to claim 1 or 2.
7. A transition metal phosphine complex according to claim 5 or 6,
wherein said transition metal is at least one transition metal
selected from the group consisting of iridium, rhodium, ruthenium,
palladium, nickel, copper and platinum.
8. An catalyst for asymmetric synthesis comprising a transition
metal phosphine complex according to any one of claims 5-7.
Description
TECHNICAL FIELD
[0001] This invention relates to novel phosphine compounds,
production intermediates thereof, transition metal complexes with
the phosphine compounds contained as ligands therein, and
transition metal complex catalysts useful as catalysts for various
asymmetric synthetic reactions.
BACKGROUND ART
[0002] Numerous reports have been published to date on transition
metal complex catalysts usable in catalytic asymmetric syntheses
such as asymmetric hydrogenation reactions, asymmetric
hydrosilylation reactions, asymmetric hydroformylation reactions
and asymmetric isomerization reactions. Among these, transition
metal complexes of ruthenium, iridium, rhodium, palladium, nickel
or the like, which contain optically active phosphines as ligands,
have been reported to possess excellent performance as catalysts
for asymmetric synthetic reactions, and some of them are already
used in the industrial application [Asymmetric Catalysis in Organic
Synthesis, Ed., R. Noyori, Wiley & Sons (1994)].
[0003] Phosphole compounds, meanwhile, have been extensively
studied for many years with respect to their syntheses and physical
properties, but there are still few instances confirming the fact
that phosphole compounds were applied to syntheses or asymmetric
reactions of optically active substances.
[0004] In recent years, some optically active diphosphine ligands
each containing one or more phosphole moieties have been reported,
and have also been applied to asymmetric hydrogenation reactions
(J. Mol. Cat., 72, 21-25, 1992; Organometallics, 20, 1014-1019,
2001).
[0005] Among the compounds reported so far are chiral transition
metal complexes of chiral bis(phosphorane) obtained using chiral
1,4-diol cyclic sulfate esters as precursors (JP 6-508848 A),
diphosphine derivatives (JP 7-149777 A), diphosphole derivatives
(JP 2002-527444 A), isophosphindolinic acids (JP 2002-527445 A),
etc.
[0006] However, these optically active diphosphine ligands, each of
which contains one or more phosphole moieties, are not yet free
from the problems associated with the industrial viewpoint, because
their syntheses are all required to go through cleavage by metallic
lithium of carbon-phosphorus bonds in the corresponding
1-phenylphosphole compounds.
[0007] Moreover, these ligands require improvements of catalysts if
they are not sufficient in selectivity (chemical selectively,
enantio-selectivity) and catalytic activities, depending on this
reaction targets or their reaction substrates.
DISCLOSURE OF THE INVENTION
[0008] An object of the present invention is to provide a novel
phosphine compound and also, an asymmetric synthesis catalyst which
contains a transition metal phosphine complex with the phosphine
compound contained as a ligand therein and which has excellent
performance in chemical selectivity, enantio-selectivity, catalytic
activities and the like as a catalyst for asymmetric synthetic
reactions, especially for asymmetric hydrogenation reactions.
[0009] To solve the above-described problems, the present inventors
have carried out extensive researches. As a result, it has been
found that transition metal catalysts containing primary phosphines
of a particular construction, especially phosphine compounds
derived from axially asymmetric, pave the way to solve the overall
problems left to asymmetric hydrogenation reactions. Thus, the
present invention was accomplished.
[0010] In one aspect of the present invention, there is thus
provided a phosphine compound represented by the following formula
(1): 2
[0011] In the above formula (1), R.sup.1 and R.sup.2 each
independently represents a hydrogen atom, a substituted or
unsubstituted C.sub.1-10 alkyl group, a substituted or
unsubstituted C.sub.1-10 alkoxy group, a substituted or
unsubstituted C.sub.2-10 alkenyl group, a substituted or
unsubstituted di(C.sub.1-5 alkyl)amino group, a substituted or
unsubstituted, 5- to 8-membered cyclic amino group, a substituted
or unsubstituted, 5-to 8-membered alicyclic group, a substituted or
unsubstituted aryl group, a substituted or unsubstituted aralkyl
group, a substituted or unsubstituted heterocyclic group, a
trisubstituted silyl group or a halogen atom. R.sup.3, R.sup.4,
R.sup.5 and R.sup.6 each independently represents a hydrogen atom,
a C.sub.1-5 alkyl group, a C.sub.1-5 alkoxy group, a
di(C.sub.1-5alkyl) amino group, a 5- to 8-membered cyclic amino
group or a halogen atom. R.sup.7 represents a C.sub.1-5 alkyl
group, a C.sub.1-5 alkoxy group, a di(C.sub.1-5 alkyl)amino group,
a 5- to 8-membered cyclic amino group or a halogen atom. R.sup.3
and R.sup.4, R.sup.5 and R.sup.6, and R.sup.6 and R.sup.7 may each
be fused together to form a fused benzene ring, a fused,
substituted benzene ring, a trimethylene group, a tetramethylene
group, a pentamethylene group, a methylenedioxy group, an
ethylenedioxy group or a trimethylenedioxy group.
[0012] In other aspects of the present invention, there are also
provided a transition metal phosphine complex with the phosphine
compound, which is represented by the formula (1), contained as a
ligand therein; and also an asymmetric synthesis catalyst
containing the transition metal phosphine complex.
[0013] In a still further aspect of the present invention, there is
also provided a primary phosphine compound represented by the
following formula (2): 3
[0014] wherein R.sup.5, R.sup.6 and R.sup.7 have the same meanings
as defined above.
[0015] Incidentally, an optically active, primary phosphine having
the biaryl skeleton is referred to in JP 6-508848 A, which however
discloses nothing more than a mere chemical structure and makes no
mention whatsoever about its production process, to say nothing
about a description on an optically active substance.
[0016] The novel phosphine compound according to the present
invention is useful especially as a ligand in a transition metal
complex. The transition metal phosphine complex, on the other hand,
is useful as a catalyst for asymmetric synthetic reactions. The
novel phosphine compound useful as a ligand can be prepared by a
relatively economical preparation process. Further, use of this
catalyst makes it possible to obtain an asymmetric hydride of high
optical purity with good yield so that this catalyst is also
extremely useful from the industrial standpoint.
BEST MODES FOR CARRYING OUT THE INVENTION
[0017] The present invention will hereinafter be described in
detail.
[0018] In the phosphine compound of the present invention
represented by the formula (1), specific examples of the C.sub.1-10
alkyl group represented by R.sup.1 or R.sup.2 can include methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. These
alkyl groups may each contain, as substituent(s), 1 to 4 functional
groups which are inert to asymmetric synthetic reactions.
Illustrative of the substituent (s) are hydroxyl; C.sub.1-4 alkoxy
groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
isobutoxy, sec-butoxy and tert-butoxy; and halogen atoms such as
fluorine, chlorine, bromine and iodine.
[0019] Specific examples of the C-.sub.1-10 alkoxy group
represented by R.sup.1 or R.sup.2 can include methoxy, ethoxy,
n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy,
tert-butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy and
decyloxy. These alkoxy groups may each contain, as substituent(s),
1 to 4 functional groups which are inert to asymmetric synthetic
reactions. Illustrative of the substituent(s) are C.sub.1-4 alkyl
groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, sec-butyl and tert-butyl; hydroxyl; C.sub.1-4 alkoxy
groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
isobutoxy, sec-butoxy and tert-butoxy; and halogen atoms such as
fluorine, chlorine, bromine and iodine.
[0020] Specific examples of the C.sub.2-10 alkenyl group
represented by R.sup.1 or R.sup.2 can include vinyl, allyl,
1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 2-methylallyl,
pentenyl, hexenyl, heptenyl, octenyl, nonenyl, and decenyl. These
alkenyl groups may each contain, as substituent (s), 1 to 4
functional groups which are inert to asymmetric synthetic
reactions. Illustrative of the substituent(s) are C.sub.1-4 alkyl
groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, sec-butyl and tert-butyl; hydroxyl; C.sub.1-4 alkoxy
groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
isobutoxy, sec-butoxy and tert-butoxy; phenyl; and halogen atoms
such as fluorine, chlorine, bromine and iodine.
[0021] Specific examples of the di(C.sub.1-5 alkyl)amino group
represented by R.sup.1 or R.sup.2 can include dimethylamino,
diethylamino, di(n-propyl)amino, diisopropylamino,
di(n-butyl)amino, diisobutylamino, di(sec-butyl)amino,
di(tert-butyl)amino, and dipentyl amino. These di (C.sub.1-5
alkyl)amino groups may each contain, as substituent(s), 1 to 4
functional groups which are inert to asymmetric synthetic
reactions. Illustrative of the substituent(s) are hydroxyl;
C.sub.1-4 alkoxy groups such as methoxy, ethoxy, n-propoxy,
isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; and
halogen atoms such as fluorine, chlorine, bromine and iodine.
[0022] Specific examples of the 5- to 8-membered, cyclic amino
group represented by R.sup.1 or R.sup.2 can include pyrrolidino and
piperidino. These cyclic amino groups may each contain, as
substituent(s), 1 to 4 functional groups which are inert to
asymmetric synthetic reactions. Illustrative of the substituent(s)
are C.sub.1-4 alkoxy groups and halogen atoms.
[0023] Specific examples of the substituted or unsubstituted, 5- to
8-membered alicyclic group represented by R.sup.1 or R.sup.2 can
include cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
Illustrative of substituents on these 5- to 8-membered alicyclic
groups are C.sub.1-4 alkyl groups, a hydroxyl group, C.sub.1-4
alkoxy groups and halogn atoms. The alicyclic groups may each
contain 1 to 4 of these substituents. Specific examples of the
substituent(s) are C.sub.1-4 alkyl groups such as methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
hydroxyl; C.sub.1-4 alkoxy groups such as methoxy, ethoxy,
n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and
tert-butoxy; and halogen atoms such as fluorine, chlorine, bromine
and iodine.
[0024] Specific examples of the substituted or unsubstituted, aryl
group represented by R.sup.1 or R.sup.2 can include C.sub.6-10 aryl
groups such as phenyl, naphthalen-1-yl, and naphthalen-2-yl.
Illustrative of substituents on the aryl groups are C.sub.1-4 alkyl
groups, hydroxyl group, C.sub.1-4 alkoxy groups, and halogen
groups. The aryl groups may each contain 1 to 5 substituents
selected from these substituents. Specific examples of the
substituents can include C.sub.1-4 alkyl groups such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and
tert-butyl; hydroxyl; C.sub.1-4 alkoxy groups such as methoxy,
ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and
tert-butoxy; and halogen atoms such as fluorine, chlorine, bromine
and iodine.
[0025] Specific examples of the substituted or unsubstituted,
aralkyl group represented by R.sup.1 or R.sup.2 can include aralkyl
groups each having 7 to 15 carbon atoms in total, such as benzyl,
.alpha.-phenethyl, .beta.-phenethyl, .alpha.-phenylpropyl,
.beta.-phenylpropyl, .gamma.-phenylpropyl, and naphthylmethyl.
Illustrative of substituents on these aralkyl groups are C.sub.1-4
alkyl groups, hydroxyl group, C.sub.1-4 alkoxy groups, and halogen
atoms. These aralkyl groups may each contain 1 to 4 substituents
selected from these substituents. Specific examples of the
substituents can include C.sub.1-4 alkyl groups such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and
tert-butyl; hydroxyl; C.sub.1-4alkoxy groups such as methoxy,
ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and
tert-butoxy; and halogen atoms such as fluorine, chlorine, bromine
and iodine.
[0026] Specific examples of the substituted or unsubstituted,
heterocyclic group represented by R.sup.1 or R.sup.2 can include 5-
or 6-membered heterocyclic groups each of which contains 1 to 3
hetero atoms selected from nitrogen, oxygen and sulfur atoms, such
as 2-pyridyl, 2-furyl and 2-thienyl. Illustrative of substituents
on these heterocyclic groups are C.sub.1-4 alkyl groups, hydroxyl
group, C.sub.1-4 alkoxy groups, and halogen atoms. These
heterocyclic groups may each contain 1 to 4 substituents selected
from these substituents. Specific examples of the substituents can
include C.sub.1-4 alkyl groups such as methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl; hydroxyl;
C.sub.1-4 alkoxy groups such as methoxy, ethoxy, n-propoxy,
ispropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; and
halogen atoms such as fluorine, chlorine, bromine andiodine.
[0027] Specific examples of the trisubstituted silyl group
represented by R.sup.1 or R.sup.2 can include tri (C.sub.1-6 alkyl)
silyl groups such as trimethylsilyl, triethylsilyl,
triisopropylsilyl, dimethylisopropylsilyl, diethylisopropylsilyl,
dimethyl(2,3-dimethyl-2-butyl)silyl, tert-butyldimethylsilyl, and
dimethylhexylsilyl; di(C.sub.1-6 alkyl) (C.sub.6-18 aryl)silyl
groups such as dimethylcumylsilyl; di(C.sub.6-18 aryl) (C.sub.1-6
alkyl)silyl groups such as tert-butyldiphenylsilyl and
diphenylmethylsilyl; tri(C.sub.6-18 aryl)silyl groups such as
triphenylsilyl; and tri(C.sub.7-19 aralkyl)silyl groups such as
tribenzylsilyl and tri-p-xylylsilyl.
[0028] Specific examples of the halogen atom represented by R.sup.1
or R.sup.2 can include fluorine, chlorine, bromine and iodine.
[0029] Among these, preferred examples of R.sup.1 and R.sup.2 can
include hydrogen atom; C.sub.1-4 alkyl groups such as methyl,
ethyl, propyl, isopropyl, n-butyl and tert-butyl, each of which may
contain one or more substituents; alkenyl groups such as vinyl and
styryl, each of which may contain one or more substituents;
dialkylamino groups such as dimethylamino and diethylamino; 5- to
8-membered cyclic amino groups such as piperidino; C.sub.6-10 aryl
groups such as phenyl, 4-tolyl, 3,5-xylyl,
3,5-di(tert-butyl)-4-methoxyphenyl, naphthalen-1-yl and
naphthalen-2-yl, each of which may contain one or more
substituents; aralkyl groups each having 7 to 15 carbon atoms in
total, such as benzyl and .alpha.-phenylethyl; heterocyclic groups
such as 2-pyridyl, 2-furyl and 2-thienyl; and trialkylsilyl groups
such as trimethylsilyl and tert-butyldimethylsilyl.
[0030] Particularly preferred examples of R.sup.1 and R.sup.2 can
include hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl,
tert-butyl, trifluoromethyl, and phenyl.
[0031] Specific examples of the C.sub.1-5 alkyl group represented
by each of R.sup.3 to R.sup.6 can include methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and
pentyl.
[0032] Specific examples of the C.sub.1-5 alkoxy group represented
by each of R.sup.3 to R.sup.6 can include methoxy, ethoxy,
n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy
and pentoxy.
[0033] Specific examples of the di(C.sub.1-5 alkyl)amino group
represented by each of R.sup.3 to R.sup.6 can include
dimethylamino, diethylamino, di(n-propyl)amino, diisopropylamino,
di(n-butyl)amino, diisobutylamino, di(sec-butyl)amino,
di(tert-butyl)amino, and dipentylamino.
[0034] Specific examples of the 5- to 8-membered, cyclic amino
group represented by each of R.sup.3 to R.sup.6 can include
pyrrolidino and piperidino. Specific examples of the halogen atom
represented by each of R.sup.3 to R.sup.6 can include fluorine,
chlorine, bromine, and iodine.
[0035] Among these, preferred examples of R.sup.3 to R.sup.6 can
include hydrogen atom; C.sub.1-4 alkyl groups such as methyl,
ethyl, propyl, isopropyl, n-butyl, and tert-butyl; alkoxy groups
such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and
tert-butoxy; dialkylamino groups dimethylamino and diethylamino;
and 5- or 8-membered, cyclic amino groups such as pyrrolidino and
piperidino.
[0036] As particularly preferred R.sup.3 and R.sup.4, hydrogen
atoms can be mentioned.
[0037] As particularly preferred R.sup.5 and R.sup.6, hydrogen
atoms and methoxy groups can be mentioned.
[0038] Specific examples of the C.sub.1-5 alkyl group represented
by R.sup.7 can include methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, sec-butyl, tert-butyl, and pentyl.
[0039] Specific examples of the C.sub.1-5 alkoxy group represented
by R.sup.7 can include methoxy, ethoxy, n-propoxy, isopropoxy,
n-butoxy, isobutoxy, sec-butoxy, tert-butoxy and pentoxy.
[0040] Specific examples of the di(C.sub.1-5 alkyl)amino group
represented by R.sup.7 can include dimethylamino, diethylamino,
di(n-propyl)amino, diisopropylamino, di(n-butyl)amino,
diisobutylamino, di(sec-butyl)amino, di(tert-butyl)amino, and
dipentylamino.
[0041] Specific examples of the 5- to 8-membered, cyclic amino
group represented by R.sup.7 can include pyrrolidino and
piperidino.
[0042] Specific examples of the halogen atom represented by R.sup.7
can include fluorine, chlorine, bromine, and iodine.
[0043] Among these, preferred examples of R.sup.7 can include
C.sub.1-4 alkyl groups such as methyl, ethyl, propyl, isopropyl,
n-butyl, and tert-butyl; alkoxy groups such as methoxy, ethoxy,
n-propoxy, isopropoxy, n-butoxy, and tert-butoxy; dialkylamino
groups dimethylamino and diethylamino; and 5 or 8-membered, cyclic
amino groups such as pyrrolidino and piperidino.
[0044] As particularly preferred R.sup.7, methyl and methoxy can be
mentioned.
[0045] In the phosphine compound of the present invention
represented by the formula (1), R.sup.3 and R.sup.4, R.sup.5 and
R.sup.6, and R.sup.6 and R.sup.7 may each be fused together to form
a fused benzene ring, a fused, substituted benzene ring, a
trimethylene group, a tetramethylene group, a pentamethylene group,
a methylenedioxy group, an ethylenedioxy group or a
trimethylenedioxy group.
[0046] Preferred examples of such fused phosphine compounds can
include those in which R.sup.6 and R.sup.7 are fused together to
form a fused benzene ring, a fused, substituted benzene ring, a
trimethylene group, a tetramethylene group, a pentamethylene roup,
a methylenedioxy group, an ethylenedioxy group or a
trimethylenedioxy group.
[0047] Particularly preferred examples can include fused phosphine
compounds in which R.sup.6 and R.sup.7 are fused together to form a
fused benzene ring, a fused, substituted benzene ring, a
tetramethylene group, a methylenedioxy group, or an ethylenedioxy
group.
[0048] As substituents on the above-described, fused, substituted
benzene rings, functional groups inert to asymmetric synthetic
reactions can be mentioned. The fused, substituted benzene rings
may each contain 1 to 4 substituents selected from such functional
groups. Specific examples of the substituents can include C.sub.1-4
alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, sec-butyl and tert-butyl; hydroxyl; C.sub.1-4 alkoxy
groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
isobutoxy, sec-butoxy and tert-butoxy; and halogen atoms such as
fluorine, chlorine, bromine and iodine.
[0049] The phosphine compound (1) according to the present
invention is in the form of an axially asymmetric, optically active
substance (enantiomer), a racemic modification, or a mixture
thereof, with a single, axially asymmetric, optically active
substance (enantiomer) being particularly preferred.
[0050] Particularly preferred examples of the phosphine compound
(1) according to the present invention can include phosphine
compounds represented by the following formula (1'): 4
[0051] wherein R.sup.1' and R.sup.2' each independently represents
a hydrogen atom, a substituted or unsubstituted C.sub.1-5 alkyl
group or a substituted or unsubstituted aryl group; R represents a
hydrogen atom, a C.sub.1-5 alkyl group, a C.sub.1-5 alkoxy group or
a halogen atom; R.sup.7' represents a C.sub.1-5 alkyl group, a
C.sub.1-5 alkoxy group or a halogen atom; and R.sup.6' and R.sup.7'
may be fused together to form a fused benzene ring, a fused,
substituted benzene ring, a tetramethylene group, a methylenedioxy
group or an ethylenedioxy group.
[0052] In the phosphine compounds of the present invention
represented by the formula (1'), specific examples of the C.sub.1-5
alkyl group represented by R.sup.1' or R.sup.2' can include methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, and pentyl. These alkyl groups may each contain 1 to 4
substituents such as halogen atoms. As specific examples of such
substituted alkyl groups, trifluoromethyl and the like can be
mentioned.
[0053] Specific examples of the substituted or unsubstituted aryl
group reprsented by R.sup.1' or R.sup.2' can include phenyl,
naphthalen-1-yl, and naphthalen-2-yl. Illustrative of substituents
on the aryl group are C.sub.1-4 alkyl groups, hydroxyl group,
C.sub.1-4 alkoxy groups, and halogen atoms. The aryl groups may
each contain 1 to 5 substituents selected from these substituents.
Specific examples of the substituents can include C.sub.1-4 alkyl
groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, sec-butyl and tert-butyl; hydroxyl; C.sub.1-4 alkoxy
groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
isobutoxy, sec-butoxy and tert-butoxy; and halogen atoms such as
fluorine, chlorine, bromine and iodine.
[0054] Specific examples of the C.sub.1-5 alkyl groups represented
by R.sup.6' can include methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl, tert-butyl and pentyl.
[0055] Specific examples of the C.sub.1-5 alkoxy groups represented
by R.sup.6' can include methoxy, ethoxy, n-propoxy, isopropoxy,
n-butoxy, isobutoxy, sec-butoxy, tert-butoxy and pentyloxy.
[0056] Specific examples of the halogen atom represented by
R.sup.6' can include fluorine, chlorine, bromine and iodine.
[0057] Specific examples of the C.sub.1-5 alkyl groups represented
by R.sup.7' can include methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl, tert-butyl and pentyl.
[0058] Specific examples of the C.sub.1-5 alkoxy groups represented
by R.sup.7' can include methoxy, ethoxy, n-propoxy, isopropoxy,
n-butoxy, isobutoxy, sec-butoxy, tert-butoxy and pentyloxy.
[0059] Specific examples of the halogen atom represented by
R.sup.7' can include fluorine, chlorine, bromine and iodine.
[0060] R.sup.6' and R.sup.7' may be fused together to form a fused
benzene ring, a fused, substituted benzene ring, a tetramethylene
group, a methylenedioxy group or an ethylenedioxy group, with a
fused benzene ring, tetramethylene group or methylenedioxy group
being preferred.
[0061] The phosphine compounds (1') according to the present
invention are each in the form of an axially asymmetric, optically
active substance (enantiomer), a racemic modification, or a mixture
thereof, with a single, axially asymmetric, optically active
substance (enantiomer) being particularly preferred.
[0062] The primary phosphine compounds represented by the formula
(2) are intermediates for the corresponding phosphine compounds
represented by the formula (1).
[0063] As specific examples of R.sup.5, R.sup.6 and R.sup.7 in the
primary phosphine compounds represented by the formula (2), the
same groups and atoms as described above can be exemplified.
[0064] The primary phosphine compounds according to the present
invention are each in the form of an axially asymmetric, optcally
active substance (enantiomer), a racemic modification, or a mixture
thereof, with a single, axially asymmetric, optically active
substance (enantiomer) being particularly preferred.
[0065] Among the phosphine compounds of the present invention,
particularly preferred are primary phosphine compounds represented
by the following formula (2'): 5
[0066] wherein R.sup.5, R.sup.6' and R.sup.7' have the same
meanings as defined above.
[0067] The primary phosphine compounds represented by the formula
(2') are intermediates for the corresponding phosphine compounds
represented by the formula (1').
[0068] As specific examples of R.sup.5', R.sup.6' and R.sup.7' in
the primary phosphine compounds represented by the formula (2'),
the same groups and atoms as described above can be
exemplified.
[0069] The primary phosphine compounds of the present invention
represented by the formula (2') are each in the form of an axially
asymmetric, optically active substance (enantiomer), a racemic
modification, or a mixture thereof, with a single, axially
asymmetric, optically active substance (enantiomer) being
particularly preferred.
[0070] The phosphine compound (1) of the present invention can be
produced, for example, in accordance with the following 6
[0071] wherein X represents a halogen atom, preferably a bromine
atom, and R.sup.1 to R.sup.7 have the same meanings as defined
above.
[0072] Described specifically, excess diethyl chlorophosphate
((EtO).sub.2POCl) is reacted with a Grignard reagent, which has
been obtained from a compound (3) and magnesium, in an organic
solvent such as diethyl ether or tetrahydrofuran to obtain a
compound (4). In the presence of lithium diisopropylamide (LDA),
ferric chloride is reacted with the compound (4) to yield a
compound (5). The compound (5) is then reduced with trimethylsilyl
chloride (TMSCl) and lithium aluminum hydrie (LiAlH.sub.4) to
afford a primary phosphine represented by the formula (2). Further,
an alkadiyne is reacted with the primary phosphine in the presence
of an alkyllithium such as n-butyllithium or n-propyllithium to
obtain the phosphine compound (1).
[0073] Taking as an example an optically active substance of a
compound (7) represented by the following formula (7): 7
[0074] i.e., the (+)-isomer
((+)-4,4'-bi-1,3-benzodioxole)-5,5'-diylbis(2,- 5-dimethyl
1H-phosphole)), which may hereinafter be referred to as
"(+)-MP.sup.2-SEGPHOS", to avoid complexity, a production process
of the compound according to the present invention will be
described specifically. It should however be borne in mind that the
present invention is not limited to this example.
[0075] (+)-MP.sup.2-SEGPHOS can be produced by the process shown in
the following reaction scheme. 8
[0076] Wherein * indicates axially asymmetric optical activity.
[0077] A Grignard reagent, which has been prepared from
3,4-methylenedioxyphenyl bromide (3'), and diethyl chlorophosphate
are reacted to synthesize a phosphonate (4'). Ferric chloride
(FeCl.sub.3) is then added to the phosphonate (4') in the presence
of lithium diisopropylamide to yield a diphosphate (5') as a
racemic compound (see, JP 2000-16998 A, Example 4). After the
racemic modification of the diphosphate (5'), obtained as described
above, is optically resolved using (-)-toluoyltartaric
acid((-)-DTT), reduction is conducted with trimethylsilyl chloride
(TMSCl)/lithium aluminum hydride (LiAlH.sub.4) to afford
(-)-4,4'-bi-1,3-benzodioxole)-5,5'-diylbisphosphine (8)) which may
hereinafter be referred to as "(-)--H.sup.2-SEGPHOS". Finally, the
compound (8) is reacted with 2,4-hexadiyne in the presence of
n-butyllithium to yield the target compound, (+)-MP.sup.2-SEGPHOS
((+)-(7)).
[0078] Further, (+)--H.sup.2-SEGPHOS is obtained by conducting
optical resolution with (+)-toluoyltartaric acid, while
(-)-MP.sup.2-SEGPHOS is obtained with (+)--H.sup.2-SEGPHOS.
[0079] The optical active compound (7) can be obtained from recemic
compound (7) using optically active column or the like. The optical
active compound (2), on the other hand, can also be obtained from
recemic compound (2) using optically active column or the like.
[0080] Concerning the compounds in which R.sup.1 and R.sup.2 are
other than methyl groups, the target compounds can be obtained
using the corresponding alkadiynes in place of 2,4-hexadiyne.
Illustrative of the corresponding alkadiynes are 3,5-octadiyne,
4,6-decadiyne, 2,7-dimethyl-3,5-octadiyne, 5,7-dodecadiyne,
3,8-dimethyl-4,6-decadiyne, 2,9-dimethyl-4,6-decadiyne,
2,2,7,7-tetramethyl-3,5-octadiyne, 6,8-tetradecadiyne,
4,9-diemthyl-5,7-dodecadiyne, 2,11-dimethyl-5,7-dodec- adiyne,
1,1,1,6,6,6-hexafluoro-2,4-hexadiyne, 1,3-diphenylbutadiyne,
1,3-bis(4-tolyl)-butadiyne, 1,3-bis(3,5-xylyl)-butadiyne,
1,3-bis(naphthalen-1-yl)-butadiyne,
1,3-bis(naphthalen-2-yl)-butadiyne, and
1,3-bis(3,5-di(tert-butyl)-4-methoxyphenyl)-butadiyne.
[0081] The phosphine compounds (1) of the present invention and the
primary phosphine compounds of the present invention represented by
the formula (2), which are other than those containing a hydrogen
atom as R.sup.5 and a methylenedioxy group as a fused group formed
by R.sup.6 and R.sup.7, can be produced by using, instead of
3,4-methyleriedioxyphenyl bromide, other aryl halogenides. Specific
examples can include 3-methoxyphenyl bromide, 3-ethoxyphenyl
bromide, 3-methylphenyl bromide, 3-ethylphenyl bromide,
3,4-ethylenedioxyphenyl bromide, 3,4-trimethylenedioxyphenyl
bromide, and 2-naphthyl bromide.
[0082] The above-described process can be similarly used to obtain
the phosphine compounds (1) and primary phosphine compounds
represented by the formula (2) other than those containing methyl
groups as R.sup.1 and R.sup.2, hydrogen atoms as R.sup.3, R.sup.4
and R.sup.5 and a methylenedioxy group as a fused group formed by
R.sup.6 and R.sup.7.
[0083] The phosphine compounds (1) of this invention obtained as
described above, as ligands, form transition metal phosphine
complexes. Examples of transition metals useful in forming these
complexes can include iridium, rhodium, ruthenium, palladium,
nickel, copper and platinum. Preferred examples of complexes so
formed can include transition metaphosphine complexes represented
by the following formula (9):
[M.sub.mL.sub.nW.sub.pU.sub.q].sub.rZ.sub.s (9)
[0084] wherein M is a transition metal selected from the group
consisting of iridium, rhodium, ruthenium, palladium, nickel,
copper and platinum; L is a phosphine compound represented by the
formula (1); W, U, m, n, p, q, r and s are (a) when M is iridium or
rhodium, (i) W is chlorine, bromine or iodine, m=n=p=1, r=2, and
q=s=0, (ii) W is 1,5-cyclooctadiene or norbonadiene, Z is BF.sub.4,
ClO.sub.4, OTf (Tf: triflate group (SO.sub.3CF.sub.3)), PF.sub.3,
SbF.sub.6 or BPh.sub.4 (Ph: phenyl group), m=n=p=r=s=1, and q=0,
(iii) Z is BF.sub.4, ClO.sub.4, OTf, PF.sub.3, SbF.sub.6 or
BPh.sub.4, m=r=s=1, n=2, and q=0, (b) when M is ruthenium, (i) W is
chlorine, bromine or iodine, Z is a trialkylamine, m=p=s=1, n=r=2,
and q=0, (ii) W is chlorine, bromine or iodine, Z is a pyridyl
group or ring-substituted pyridyl group, m=n=r=1, p=2, and q=0,
(iii) W is a carboxylate group, m=n=r=1, p=2, and q=s=0, (iv) W is
chlorine, bromine or iodine, Z is dimethylformamide or
dimethylacetamide, m=n=r=1, p=2, q=0, and s stands for an integer
of from 0 to 4, (v) W is chlorine, bromine or iodine, U is
chlorine, bromine or iodine, Z is a dialkylammonium ion, m=n=p=2,
q=3, and r=s=1, (vi) W is chlorine, bromine or iodine, U is an
aromatic compound or olefin as a neutral ligand, Z is chlorine,
bromine, iodine or 13, and m=n=p=q=r=s=1, (vii) Z is BF.sub.4,
ClO.sub.4, OTf, PF.sub.6, SbF.sub.6 or BPh.sub.4, m=n=r=1, p=q=0,
and s=2, (viii) W and U may be the same or different and are each a
hydrogen atom, chlorine, bromine, carboxyl group or a still further
anion group, Z is a diamine compound, and m=n=p=q=r=s=1, (c) when M
is palladium, (i) W is chlorine, bromine or iodine, m=n=r=1, p=2,
and q=s=0, (ii) W is an allyl group, m=n=p=r=1, and q=s=0, (iii) Z
is BF.sub.4, ClO.sub.4, OTf, PF.sub.6, SbF.sub.6 or BPh.sub.4,
m=n=r=1, p=q=0, and s=2, (iv) W is a C.sub.1-5 alkylnitrile,
benzonitrile, phthalonitrile, pyridine, dimethylsulfoxide,
dimethylformamide, dimethylacetamide or acetone, Z is BF.sub.4,
ClO.sub.4, OTf, PF.sub.6, SbF.sub.6 or BPh.sub.4, m=n=r=1, p=s=2,
and q=0, (d) when M is a nickel, (i) W is chlorine, bromine or
iodine, m=n=r=1, p=2, and q=s=0, (ii) Z is BF.sub.4, ClO.sub.4,
OTf, PF.sub.6, SbF.sub.6 or BPh.sub.4, m=n=r=1, p=q=0, and s=2, (e)
when M is copper, W is hydrogen atom, fluorine, chlorine, bromine
or iodine, m=p=4, n=2, r=1, q=s=0, (f) when M is platinum, (i) W is
a C.sub.1-5 alkylnitrile, benzonitrile, phthalonitrile, pyridine,
dimethylsulfoxide, dimethylformamide, dimethylacetamide or acetone,
Z is BF.sub.4, ClO.sub.4, OTf, PF.sub.6, SbF.sub.6 or BPh.sub.4,
m=n=r=1, p=s=2, and q=0, (ii) W is chlorine, bromine or iodine,
m=n=r=1, p=2, and q=s=0, (iii) W is chlorine, bromine or iodine, U
is SnCl.sub.2, m=n=q=r=1, p=2, and s=0, and (iv) W is chlorine,
bromine or iodine, U is SnCl.sub.3, m=n=p=q=r=1, and s=0.
[0085] No particular limitation is imposed on the production
process of the transition metal phosphine complexes (9). For
example, however, they can be produced by a process to be described
next or by its equivalent process. In the formulas of transition
metal phosphine complexes to be described below, the following
abbreviations will be employed: cod: 1,5-cyclooctadine, nbd:
norbornadiene, Ac: acetyl group, acac: acetyl acetonate, dmf:
dimethylformamide, en: ethylenediamine, DPEN:
diphenylethylenediamine, and Tf: trifluoromethanesulfonyl
group.
[0086] Rhodium complexes: As a specific example of production of a
rhodium complex, it can be synthesized, for example, by reacting
bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate
([Rh(cod).sub.2] BF.sub.4) and a phosphine compound (1) of the
present invention in accordance with the procedure described in
"Jikken Kagaku Koza (Experimental Chemistry Series), 4.sup.th
edition" compiled by The Chemical Society of Japan, 18
(Organometallic Complexes), 339-344, 1991 (Maruzen).
[0087] Specific examples of rhodium complexes can include
[Rh(L)Cl].sub.2, [Rh(L)Br].sub.2, [Rh(L)I].sub.2, [Rh(cod)(L)]OTf,
[Rh(cod)(L)]BF.sub.4, [Rh(cod)(L)]ClO.sub.4, [Rh(cod)(L)]SbF.sub.6,
[Rh(cod)(L)]PF.sub.6, [Rh(cod)(L)]BPh.sub.4, [Rh(nbd)(L)]OTf,
[Rh(nbd)(L)]BF.sub.4, [Rh(nbd)(L)]ClO.sub.4, [Rh(nbd)(L)]SbF.sub.6,
[Rh(nbd)(L)]PF.sub.6, [Rh(nbd)(L)]BPh.sub.4, [Rh(L).sub.2]OTf,
[Rh(L).sub.2]BF.sub.4, [Rh(L).sub.2]ClO.sub.4,
[Rh(L).sub.2]SbF.sub.6, [Rh(L).sub.2]PF.sub.6, and
[Rh(L).sub.2]BPh.sub.4.
[0088] Ruthenium complexes: As a process for producing a ruthenium
complex, it can be prepared, for example, by heating
(1,5-cyclooctadiene) dichlororuthenium ([Ru(cod)Cl.sub.2].sub.n)
and a phosphine compound (1) of the present invention under reflux
in the presence of a trialkylamine in an organic solvent in
accordance with the procedure described in a journal (J. Chem.
Soc., Chem. Commun., 922, 1985). It can also be produced, for
example, by heating bis[dichloro(benzene)ruthenium]
([Ru(benzene)Cl.sub.2].sub.2) and a phosphine compound (1) of the
present invention in the presence of a dialkylamine under reflux in
an organic solvent in accordance with the procedure described in JP
11-269185 A. It can also be produced, for example, by heating
bis[diiodo(para-cymene)ruth- enium] ([Ru(p-cymene)I.sub.2].sub.2)
and a phosphine compound (1) of the present invention under
stirring in an organic solvent in accordance with the procedure
disclosed in a journal (J. Chem. Soc., Chem. Commun., 1208, 1989).
Further, it can also be synthesized, for example, by reacting
Ru.sub.2Cl.sub.4(L).sub.2NEt.sub.3, which has been obtained
following the procedure of a journal (J. Chem. Soc., Chem. Commun.,
992, 1985), and a diamine compound in an organic solvent in
accordance with the procedure disclosed in JP 11-189600 A.
[0089] Specific examples of ruthenium complexes can include
Ru(OAc).sub.2(L), Ru(OCOCF.sub.3).sub.2(L),
Ru.sub.2Cl.sub.4(L).sub.2NEt.- sub.3,
[[RuCl(L)].sub.2(.mu.-Cl).sub.3][Me.sub.2NH.sub.2],
[[RuBr(L)].sub.2(.mu.-Br).sub.3][Me.sub.2NH.sub.2],
[[RuI(L)].sub.2(.mu.-I).sub.3][Me.sub.2NH.sub.2],
[[RuCl(L)].sub.2(.mu.-C- l).sub.3][Et.sub.2NH.sub.2],
[[RuBr(L)].sub.2(.mu.-Br).sub.3][Et.sub.2NH.s-
ub.2][[RuI(L)].sub.2(.mu.-I).sub.3][Et.sub.2NH.sub.2],
RuCl.sub.2(L), RuBr.sub.2(L), RuI.sub.2(L), [RuCl.sub.2(L)]
(dmf).sub.n, RuCl.sub.2(L)(pyridine).sub.2,
RuBr.sub.2(L)(pyridine).sub.2, RuI.sub.2(L)(pyridine).sub.2,
RuCl.sub.2(L)(2,2'-dipyridine), RuBr.sub.2(L)(2,2'-dipyridine),
RuI.sub.2(L)(2,2'-dipyridine), [RuCl(benzene)(L)]Cl,
[RuBr(benzene)(L)]Br, [RuI(benzene)(L)]I, [RuCl(p-cymene)(L)]Cl,
[RuBr(p-cymene)(L)]Br, [RuI(p-cymene)(L)]I,
[RuI(p-cymene)(L)]I.sub.3, [Ru(L)](OTf).sub.2,
[Ru(L)](BF.sub.4).sub.2, [Ru(L)](ClO.sub.4).sub.2,
[Ru(L)](SbF.sub.6).sub.2, [Ru(L)](PF.sub.6).sub.2,
[Ru(L)](BPh.sub.4).sub.2, [RuCl.sub.2(L)](en), [RuBr.sub.2(L)](en),
[RuI.sub.2(L)](en), [RuH.sub.2(L)](en), [RuCl.sub.2(L)](DPEN),
RuBr.sub.2(L)](DPEN), [RuI.sub.2(L)](DPEN), and
[RuH.sub.2(L)](DPEN).
[0090] Iridium complexes: As a process for producing an iridium
complex, it can be prepared, for example, by reacting a phosphine
compound (1) of the present invention and
[(1,5-cyclooctadiene)(acetonitrile)iridium] tetrahydroborate
([Ir(cod)(CH.sub.3CN).sub.2]B.sub.4) under stirring in an organic
solvent in accordance with the procedure described in a journal (J.
Organomet. Chem., 428, 213, 1992).
[0091] Specific examples of iridium complexes can include
[Ir(L)Cl].sub.2, [Ir(L)Br].sub.2, [Ir(L)I].sub.2, [Ir(cod)(L)]OTf,
Ir(cod)(L)]BF.sub.4, [Ir(cod)(L)]ClO.sub.4, [Ir(cod)(L)]SbF.sub.6,
[Ir(cod)(L)]PF.sub.6, [Ir(cod)(L)]BPh.sub.4, [Ir(nbd)(L)]OTf,
[Ir(nbd)(L)]BF.sub.4, [Ir(nbd)(L)]ClO.sub.4, [Ir(nbd)(L)]SbF.sub.6,
[Ir(nbd)(L)]PF.sub.6, [Ir(nbd)(L)]BPh.sub.4, [Ir(L).sub.2]OTf,
[Ir(L).sub.2]BF.sub.4, [Ir(L).sub.2]ClO.sub.4,
[Ir(L).sub.2]SbF.sub.6, [Ir(L).sub.2]PF.sub.6,
[Ir(L).sub.2]BPh.sub.4, IrCl(cod)(CO)(L), IrBr(cod)(CO)(L), and
IrI(cod) (CO)(L).
[0092] Palladium complexes: As a process for producing a palladium
complex, it can be prepared, for example, by reacting a phosphine
compound (1) of the present invention and .pi.-allylpalladium
chloride ([(.pi.-allyl]PdCl).sub.2) in accordance with the
procedure described in journals (J. Am. Chem. Soc., 113, 9887,
1991; J. Chem. Soc., Dalton, Trans., 2246-2249, 1980; Tetrahedron
Letters, 37, 6351-6354, 1996).
[0093] Specific examples of palladium complexes can include
PdCl.sub.2(L), PdBr.sub.2(L), PdI.sub.2(L), Pd(OAc).sub.2(L),
Pd(OCOCF.sub.3).sub.2(L), [(.pi.-allyl)Pd(L)]Cl,
[(.pi.-allyl)Pd(L)]Br, [(.pi.-allyl)Pd(L)]I,
[(.pi.-allyl)Pd(L)]OTf, [(.pi.-allyl)Pd(L)]BF.sub.4,
[(.pi.-allyl)Pd(L)]ClO.sub.4, [(.pi.-allyl)Pd(L)]SbF.sub.6,
[(.pi.-allyl)Pd(L)]PF.sub.6, [(.pi.-allyl)Pd(L)]BPh.sub.4,
[(Pd(L))](OTf).sub.2, [(Pd(L))](BF.sub.4).sub.2,
[(Pd(L))](ClO.sub.4).sub- .2, [[(Pd(L))](SbF.sub.6).sub.2,
[(Pd(L))](PF.sub.6).sub.2, [(Pd(L))](BPh.sub.4).sub.2,
PhCH.sub.2Pd(L)Cl, PhCH.sub.2Pd(L)Br, PhCH.sub.2Pd(L)I, PhPdCl(L),
PhPdBr(L), PhPdI(L), Pd(L), and
[Pd(L)(PhCN).sub.2](BF.sub.4).sub.2.
[0094] Nickel complexes: As a process for producing a nickel
complex, it can be prepared, for example, by dissolving a phosphine
compound (1) of the present invention and nickel chloride
(NiCl.sub.2) in an organic solvent and heating the resultant
mixture under stirring in accordance with the procedure described
in "Jikken Kagaku Koza (Experimental Chemistry Series), 4th
edition" compiled by the Chemical Society of Japan, 18
(Organometallic Complexes), 376, 1991 (Maruzen) or the procedure
described in a journal (J. Am. Chem. Soc., 113, 9887, 1991).
[0095] Specific examples of nickel complexes can include
NiCl.sub.2(L), NiBr.sub.2(L), and NiI.sub.2(L).
[0096] Copper complexes: As a process for producing a copper
complex, it can be prepared, for example, by dissolving a phosphine
compound (1) of the present invention and copper(I) chloride
(CuCl.sub.2) in an organic solvent and heating the resultant
mixture under stirring in accordance with the procedure described
in "Jikken Kagaku Koza (Experimental Chemistry Series), 4th
edition" compiled by The Chemical Society of Japan, 18
(Organometallic Complexes), 444-445, 1991 (Maruzen).
[0097] Specific examples of copper complexes can include
Cu.sub.4F.sub.4(L).sub.2, Cu.sub.4Cl.sub.4(L).sub.2,
Cu.sub.4Br.sub.4(L).sub.2, Cu.sub.4I.sub.4(L).sub.2, and
Cu.sub.4H.sub.4(L).sub.2.
[0098] Platinum complexes: As a process for producing a platinum
complex, it can be prepared, for example, by dissolving a phosphine
compound (1) of the present invention and dibenzonitrile
dichloroplatinum (PtCl.sub.2(PhCN).sub.2) in an organic solvent and
heating the resultant mixture under stirring in accordance with the
procedure described in a journal (Organometallics, 10, 2046, 1991).
A Lewis acid (SnCl.sub.2 or the like) may be added as needed.
[0099] Specific examples of platinum complexes can include
PtCl.sub.2(L), PtBr.sub.2(L), PtI.sub.2(L),
PtCl.sub.2(L)(SnCl.sub.2), and PtCl(L)(SnCl.sub.3).
[0100] The transition metal phosphine complexes, which contain as
ligands the optically active compounds (especially, enantiomers) of
the phosphine compounds (1) of the present invention, are useful as
transition metal complex catalysts for asymmetric synthesis
reactions, especially as transition metal complex catalysts for
asymmetric hydrogenation reactions, transition metal complex
catalysts for asymmetric isomerization reactions, transition metal
complex catalysts for asymmetric hydroformylation reactions, and
the like. In the phosphine compounds (1) of the present invention,
their racemic modifications are also useful as production
intermediates for their corresponding, optically active
compounds.
[0101] When these transition metal phosphine complexes are used as
catalysts, the complexes may be used without purification although
they may be used after heightening them in purity.
[0102] These transition metal phosphine complexes, especially
transition metal phosphine complexes--each of which contains
ruthenium and
(4,4'-bi-1,3-benzodioxole)-5,5'-diylbis(2,5-dimethylphosp hole)
(MP.sup.2-SEGPHOS), an optically active compound, as a ligand--can
provide higher enantio-selectively than complexes--each of which
contains BINAP or SEGPHOS, an optically active compound having a
similar biaryl moiety, as a ligand--in asymmetric hydrogenation of
N-acetamidocinnamic acid.
[0103] When conducting asymmetric hydrogenation reactions by using
transition metal phosphine complexes of the present invention,
substrates to be subjected to asymmetric hydrogenation can be
carbonyl compounds, imines, and olefins. Specific examples can
include .alpha.-ketoesters, .beta.-ketoesters, .gamma.-ketoesters,
.alpha.-hydroxyketones, .beta.-hydroxyketones, allylketones,
.alpha.,.beta.-unsaturated ketones, enamides, enol esters, allyl
alcohols and .alpha.,.beta.-unsaturated carboxylic acids, with
.alpha.,.beta.-unsaturated carboxylic acids being preferred.
[0104] Upon conducting an asymmetric hydrogenation reaction with a
transition metal phosphine complex of the present invention,
reaction conditions cannot be specified in a wholesale manner
because they can vary depending on the substrate to be used, the
complex and the like. In general, however, the reaction may be
conducted at a reaction temperature of from 0 to 100.degree. C.
under a hydrogen pressure of from 1.0 to 10.0 MPa for 2 to 30
hours. The transition metal phosphine complex of the present
invention can be used at a molar ratio of from 1/500 to 1/10,0000
or so relative to the substrate. Any reaction solvent can be used
insofar as it is stable and gives no adverse effect to the
substrate or the reaction product. Specific examples of the
reaction solvent can include lower alcohols such as methanol,
ethanol and isopropanol, ethers such as tetrahydrofuran, and
halogenated hydrocarbons such as methylene chloride and
chlorobenzene. The amount of the reaction solvent to be used cannot
be specified in a wholesale manner because it can vary depending on
the solubility of the substrate and other parameters. In general,
however, the reaction solvent can be used in a volume (mL/g)
approximately 0.1 to 100 times as much as the weight part of the
substrate.
EXAMPLES
[0105] Based on Examples, the present invention will hereinafter be
described in detail. It should, however, be borne in mind that the
present invention is by no means limited by the Examples. The
following instruments were used in the measurement of physical
properties in each Example.
[0106] .sup.1HNMR: NMR spectrometer "DRX500 (500 MHz)" (trade name)
manufactured by Bruker BioSpin Corporation.
[0107] .sup.1P NMR: NMR spectrometer "DRX500 (202 MHz)" (trade
name) manufactured by Bruker BioSpin Corporation.
[0108] Melting point: Micro melting point meter "MP-500D" (trade
name) manufactured by Yanaco Analytical Instruments Corp.
[0109] Rotation: Optical rotation meter "DIP-4" (trade name)
manufactured by JASCO.
[0110] Gas chromatography: Gas chromatograph "5890-II" (trade name)
manufactured by Hewlett-Packard Company.
[0111] High-performance liquid chromatography: HPLC "HP1100" (trade
name) manufactured by Hewlett-Packard Company.
[0112] Mass spectrometry: Mass spectrometer "M-80B" (trade name)
manufactured by Hitachi, Ltd.
Example 1
[0113] Synthesis of
(+)-(4',4'-bi-1,3-benzodixol)-5,5'-diylbis(2,5-dimethy-
lphosphole)((+)-MP.sup.2-SEGPHOS)
[0114] (a) Synthesis of
(-)-(4',4'-bi-1,3-benzodixol)-5,5'-diylbis(diethyl-
phosphonate)((-)-5')
[0115] To a mixture of a diphosphate (6) (204.5 g, 478 mmol), which
had been obtained by the procedure disclosed in Example 4 of JP
2000-16998 A, and (-)-ditoluoyltartaric acid (153.6 g, 478 mmol),
butyl acetate (510 mL) was added, followed by heating to
105.degree. C. The reaction mixture was allowed to cool down to
room temperature. After stirred overnight, the resulting solid was
collected by filtration. Dichloromethane (1,000 mL) and a 1 mol/L
aqueous solution of sodium hydroxide (1,000 mL) were added. The
resulting mixture was stirred for 0.5 hour, and was then allowed to
separate into layers. The organic layer was washed successively
with water and a saturated aqueous solution of sodium chloride, and
was then dried over anhydrous sodium sulfate. The solvent was
distilled off to afford the title compound (55.0 g) of 98.2% ee
optical purity.
[0116] To the whole title compound (55.0 g, 106 mmol) so obtained,
(-)-ditoluoyltartaric acid (41.3 g, 106 mmol) and butyl acetate
(137 mL) were added, and the resulting mixture was heated under
reflux. After the reaction mixture was allowed to cool down in the
air, the resulting solid was collected by filtration, followed by
the addition of dichloromethane (500 mL) and a 1 mol/L aqueous
solution of sodium hydroxide (500 mL). Subsequent to mixing for 0.5
hour, the organic layer was washed successively with a 1 mol/L
aqueous solution of sodium hydroxide, water and brine, and was then
dried over anhydrous sodium sulfate. The solvent was distilled off
under reduced pressure to afford the title compound (43.7 g) of
>99.9% ee optical purity (yield: 21%). The optical purity was
measured by HPLC.
[0117] [.alpha.]D24: -50.5 (c 1.0, CHCl.sub.3)
[0118] (b) Synthesis of
(-)-(4',4'-bi-1,3-benzodixol)-5,5'-diylbisphosphin- e
((-)--H.sup.2-SEGPHOS:(-)-8)
[0119] A solution of lithium aluminum hydride (19.3 g, 50.9 mmol)
in tetrahydrofuran was cooled to -30.degree. C., into which
chlorotrimethylsilane (64.7 mL, 50.9 mmol) was added dropwise while
maintaining the resulting mixture below -20.degree. C. After the
mixture was stirred at -30.degree. C. for 30 minutes, a solution of
the (-)-diphosphate ((-)-6) (43.7 g, 8.49 mmol) in tetrahydrofuran
(150 mL) was added. Subsequent to stirring at room temperature for
1 hour, a mixed solution composed of methanol (20 mL) and
tetrahydrofuran (60 mL) was added dropwise with care. Methanol (20
mL), water (40 mL) and a 1 mol/L aqueous solution of sodium
hydroxide were then added successively, and the mixture so prepared
was stirred. The solid was filtered off through celite, and the
solvent was distilled off under reduced pressure to afford the
title compound (22.7 g, yield: 87%, 99.8% ee). Incidentally, the
optical purity was measured using HPLC (Chiralcel OD) equipped with
an optically active column.
[0120] EI-MS: m/z 307 (M+1)+
[0121] .sup.1H NMR (CDCl.sub.3) .delta.: 3.59 (4H, d, J=203.5 Hz),
5.90 (4H, s), 6.75 (2H, d, J=7.6 Hz), 7.13 (2H, m).
[0122] .sup.31P NMR(CDCl.sub.3) .delta.: 130.3(t, J=202.4 Hz).
[0123] [.alpha.]D24: -58.0 (c 1.0, CHCl.sub.3).
[0124] (c) Synthesis of
(+)-[(4',4'-bi-1,3-benzodixol)-5,5'-diyl]bis(2,5-d-
imethylphosphole)((+)-MP.sup.2-SEGPHOS)
[0125] (-)--H.sup.2-SEGPHOS (3.4 g, 11.1 mmol) and 2,4-hexadiyne
(4.5 g, 2 eq.) were dissolved with toluene (50 mL) and
tetrahydrofuran (10 mL), followed by heating to 40.degree. C. Into
the mixture, a 1.6 mol/L solution of n-butyllithium in hexane (3.5
mL, 0.5 eq.) was added dropwise. Subsequent to stirring at
40.degree. C. for 2 hours, methanol was charged, and then, the
solvent was distilled off. The residue was purified by silica gel
chromatography to afford the title compound (604 mg, yield: 13%,
optical purity: 99.6% ee). Incidentally, the optical purity was
measured using HPLC (Chiralcel OD) equipped with an optically
active column.
[0126] Mp: 228 to 230.degree. C.
[0127] EI-MS: m/z 462 ([M]+)
[0128] .sup.1HNMR (CDCl.sub.3) .delta.: 2.00 (6H, s), 2.03 (6H, s),
5.94 (2H, d, J=1.1 Hz), 6.03 (2H, d, J=1.1 Hz), 6.30-6.53 (6H, m),
6.77 (2H, d, J=8.2 Hz).
[0129] .sup.31P NMR(CDCl.sub.3) .delta.: 3.2 (s).
[0130] [.alpha.]D24: +134.70 (c 1.0, CHCl.sub.3).
Example 2
[0131] Synthesis of
(+)-[(4',4'-bi-1,3-benzodixol)-5,5'-diyl]bis(2,5-dimet-
hylphosphole)((+)--P.sup.3-SEGPHOS)
[0132] (-)--H.sup.2-SEGPHOS (3.0 g, 9.8 mmol) and
2,4-diphenylbutadiyne (3.96 g, 19.6 mmol) were dissolved with
toluene (90 mL) and tetrahydrofuran (3 mL), followed by cooling to
0.degree. C. Into the mixture, a 1.6 mol/L solution of
n-butyllithium in hexane (2.45 mL, 3.92 mmol) was added dropwise.
Subsequent to stirring the reaction mixture at 0.degree. C. for 2
hours, the reaction mixture was heated to room temperature and then
stirred further for 2 hours. Methanol was charged, and then, the
solvent was distilled off. The residue was purified by silica gel
chromatography to afford the title compound (3.29 g, yield: 47%,
optical purity: 99.7% ee). Incidentally, the optical purity was
measured using HPLC (Chiralcel OD) equipped with an optically
active column.
[0133] EI-MS: m/z 711 (M+1)+
[0134] .sup.1H NMR (CDCl.sub.3) .delta.: 5.23 (2H, d, J=1.6 Hz),
5.57 (2H, d, J=1.6 Hz), 6.62 (2H, d, J=8.2 Hz), 6.69 (2H, td,
J=2.2, 8.2 Hz), 6.74-8.10 (24H, m).
[0135] .sup.31P NMR(CDCl.sub.3) .delta.: -1.8(s).
[0136] [.alpha.]D24: +164.3 (c 1.0, CHCl.sub.3).
Example 3
[0137] Synthesis of [Rh(cod)((+)-MP.sup.2-SEGPHOS)]OTf
[0138] (+)-MP.sup.2-SEGPHOS (50 mg, 0.108 mmol) was dissolved in
dichloromethane (3 mL), and the resulting solution was added
dropwise into a mixture of [Rh(cod).sub.2]OTf (50.6 mg, 0.108 mmol)
and dichloromethane (3 mL). Subsequent to stirring at room
temperature for 4 hours, the solvent was distilled off under
reduced pressure. The solid was washed three times with 5 ml of
hexane, and then dried under reduced pressure to afford the title
compound (90 mg).
[0139] .sup.31P NMR(CD.sub.2Cl.sub.2) .delta.: 39.6 (d, J=130.5
Hz)
Example 4
[0140] Synthesis of [RuCl(p-cymene)((+)-MP.sup.2-SEGPHOS)]Cl
[0141] (+)-MP.sup.2-SEGPHOS (50.0 mg, 0.108 mmol) and
[RuCl.sub.2(p-cymene)].sub.2 (33.1 mg, 0.054 mmol) were dissolved
in a mixture of dichloromethane (2.5 mL) and ethanol (2.5 mL), and
the resulting mixture was stirred at 50.degree. C. for 4 hours. The
solvent was then distilled off under reduced pressure to afford the
title compound (76 mg, yield: 92%).
[0142] .sup.31P NMR(CD.sub.2Cl.sub.2) .delta.: 41.4 (d, J=58.0 Hz),
45.6 (d, J=58.0 Hz).
Example 5
[0143] Synthesis of Ru(OAc).sub.2((+)-MP.sup.2-SEGPHOS)
[0144] (+)-MP.sup.2-SEGPHOS (100.0 mg, 0.216 mmol) and
[RuCl.sub.2(p-cymene)].sub.2 (66.1 mg, 0.108 mmol) were dissolved
in a mixture of dichloromethane (2.5 mL) and ethanol (2.5 mL), and
the resulting mixture was stirred at 50.degree. C. for 4 hours. The
solvent was then distilled off under reduced pressure. Sodium
acetate (53.2 mg, 0.648 mmol) and 1,4-dioxane (5 mL) were then
added, followed by overnight stirring at 100.degree. C. After the
reaction mixture was filtered, the solvent was distilled off under
reduced pressure from the filtrate to afford the title compound
(154 mg, yield: 92%).
[0145] .sup.31P NMR(CD.sub.2Cl.sub.2) .delta.: 83.4 (s).
Example 6
[0146] Synthesis of [Rh(cod)((+)--P.sup.3-SEGPHOS)]OTf
[0147] (+)--P.sup.3-SEGPHOS (50.0 mg, 0.070 mmol) was dissolved in
dichloromethane (3 mL), and the resulting solution was added
dropwise in to a mixture of [Rh(cod).sub.2]OTf (32.9 mg, 0.070
mmol) and dichloromethane (3 mL). Subsequent to stirring at room
temperature for 4 hours, the solvent was distilled off under
reduced pressure. The solid was washed three times with 5 ml of
hexane, and then dried under reduced pressure to afford the title
compound (79 mg).
[0148] .sup.31P NMR(CD.sub.2Cl.sub.2) .delta.: 24.7 (d, J=136.1
Hz).
Example 7
[0149] Asymmetric Hydrogenation Reaction of N-acetamidocinnamic
Acid
[0150] Under a nitrogen atmosphere, [RuCl(p-cymene)(L)]Cl (0.0024
mmol), N-acetamidocinnamic acid (100 mg, 0.487 mmol), sodium
methoxide (29.1 mg, >95%, 0.511 mmol) and methanol (1 mL) were
charged in a stainless steel autoclave, and under conditions of
60.degree. C. and 3.0 MPa hydrogen pressure, the contents were
stirred for 15 hours. The conversion and optical purity of the
reaction product were determined by .sup.1H NMR (CD.sub.3OD) and
HPLC, respectively. As a comparative example, a similar reaction
was conducted using a similar ruthenium complex catalyst as that
employed in the above asymmetric hydrogenation except for the
replacement of L by (S)-SEGPHOS.
[0151] The results are presented in Table 1.
1 TABLE 1 Conversion Optical L (%) purity (% ee) Example 7 (+)
-MP.sup.2-SEGPHOS 83 60 Comp. Ex. (S) -SEGPHOS >99 28
[0152] In Example 7 in which hydrogenation was conducted using the
transition metal complex catalyst with MP.sup.2-SEGPHOS of the
present invention contained as a ligand therein, the optical purity
was 60% ee, that is, was excellent. Moreover, the conversion was
83%, which can be considered to be a sufficiently high value. This
conversion is in such a range that use of a little longer reaction
time can bring it to an industrially acceptable level. In the
comparative example in which hydrogenation was conducted by using
SEGPHOS having a similar biaryl skeleton, the optical purity was
28% ee, that is, extremely low although the conversion was higher
than 99%, that is, superb. From the above-described results, it is
understood that MP.sup.2-SEGPHOS according to the present invention
is an extremely useful ligand in conducting asymmetric
hydrogenation.
* * * * *